US4273864A - Color photographic light-sensitive materials - Google Patents

Color photographic light-sensitive materials Download PDF

Info

Publication number
US4273864A
US4273864A US06/105,485 US10548579A US4273864A US 4273864 A US4273864 A US 4273864A US 10548579 A US10548579 A US 10548579A US 4273864 A US4273864 A US 4273864A
Authority
US
United States
Prior art keywords
group
color photographic
formula
photographic material
coupler
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US06/105,485
Other languages
English (en)
Inventor
Tsutomu Hamaoka
Masakazu Morigaki
Satoru Sawada
Takayoshi Kamio
Kotaro Nakamura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Assigned to FUJI PHOTO FILM CO., LTD. reassignment FUJI PHOTO FILM CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HAMAOKA TSUTOMU, KAMIO TAKAYOSHI, MORIGAKI MASAKAZU, NAKAMURA KOTARO, SAWADA SATORU
Application granted granted Critical
Publication of US4273864A publication Critical patent/US4273864A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39232—Organic compounds with an oxygen-containing function

Definitions

  • the present invention relates to silver halide color photographic light-sensitive materials and, particularly, to the prevention of fading of magenta dye image obtained by development of color photographic light-sensitive materials comprising 3-anilino-5-pyrazolone type magenta type magenta couplers with a p-phenylenediamine type color developer and to prevention of discoloration of uncolored parts (referred to as white areas hereafter).
  • color images obtained by photographic processing of silver halide color photographic light-sensitive materials are composed of azomethine dyes or indoaniline dyes formed by the reaction of oxidation products of aromatic primary amine developing agents and couplers.
  • the obtained color photographic images are stored or exhibited for a long period of time.
  • heat or humidity since they are not always stable to light, heat or humidity, fading or discoloration of the dye images or discoloration of white areas generally results in deterioration of image quality, when they are exposed to light for a long period of time or stored at a high temperature and a high humidity.
  • couplers having a low fading property to use fading inhibitors to prevent fading by light or to use ultraviolet ray absorbing agents to prevent deterioration of images by ultraviolet rays.
  • couplers having a low fading property to use fading inhibitors to prevent fading by light or to use ultraviolet ray absorbing agents to prevent deterioration of images by ultraviolet rays.
  • known methods use magenta couplers such as described in U.S. Pat. No. 3,519,429, o-hydroxycoumarins such as described in U.S. Pat. No. 3,432,300, fading inhibitors having a phenolic hydroxyl group such as described in U.S. Pat. No. 3,698,909, and alkyl ethers such as described in Japanese Patent Application (OPI) No. 77526/78.
  • An object of the present invention is to provide color photographic light-sensitive materials in which color images obtained from 3-anilino-5-pyrazolone type couplers are stabilized and color contamination of the white areas is remarkably limited by incorporating a dye image stabilizing agent having a sufficient fading preventing effect or prevent discoloration of the dye image without deteriorating the color hue or fogging the photographic light-sensitive layer.
  • R 1 and R 2 each represent a tertiary alkyl group having 4 to 20 carbon atoms inclusive of carbon atoms inclusive of carbon atoms in the substituent, (for example, tertbutyl, tert-pentyl, tert-hexyl or tert-octyl, etc.) which may be substituted by an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, or halogen atoms.
  • the compounds of the present invention represented by the formula (I) can be synthesized by a process which comprises introducing tertiary alkyl groups into corresponding alkyl hydroquinone after methylation or a process which comprises methylating hydroquinone after the introduction of the tertiary alkyl groups.
  • the compounds used in the present invention have very high solubility in solvents having a high boiling point such as dibutyl phthalate or tricresyl phosphate, etc. and do not separate during storage.
  • the compounds used in the present invention do not cause fog and prevent fading of magenta dye images and discoloration of the white areas. Accordingly, they are dye image stabilizing agents which exhibit an excellent effect.
  • this effect is peculiar since it is notably shown with benzenes having methoxy groups at the 1 and 4 positions and tertiary alkyl groups at positions ortho to them but is not shown with benzenes having hydroxyl groups, ethoxy groups, butoxy groups or other alkoxy groups at the 1 and 4 positions and/or primary or secondary alkyl groups at positions ortho to them.
  • the amount of the compounds used in the present invention varies with the coupler combined therewith, however, a preferred amount is about 0.5 to 200% by weight and most preferably 2 to 150% by weight based on the coupler. Amounts lower than this are not suitable for practical use, because the fade preventing or coloration of the white areas is very poor. If higher amounts are used, there is a possibility of impeding development and to deteriorate the color density.
  • known fading inhibitors may be used together with the compounds of formula (I). Further, the compounds of formula (I) may be used alone or in combinations of two or more.
  • Examples of conventional fading inhibitors which can be combined with Compound (I) are phenol compounds such as 2,6-di-tert-butylphenol derivatives like 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol and 4-hydroxymethyl-2,6-di-tert-butylphenol; gallic acid derivatives like ethyl gallate and propyl gallate; p-alkoxyphenol derivatives like 2-(tert)-butyl-4-methoxyphenol and 4-benzyloxy-2-(tert)-octylphenol, bis-phenol derivatives like 2,2'-methylenebis(6-(tert)-butyl-4-methylphenol) and 1,1'-bis(4-hydroxyphenyl)cyclohexane; O-hydroxybenzylamine derivatives like 2-hydroxy-3-methoxybenzylamine-N,N-diacetic acid; aminophenol derivatives like 4-aminophenol, 4-phen
  • magenta coupler is used in an amount of 5 to 50 mol%, preferably 10 to 30 mol% per mol of silver halide.
  • 3-anilino-5-pyrazolone magenta couplers used in the present invention include compounds represented by the following general formula (II) ##STR4##
  • X represents a straight chain, branched chain or cyclic alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, a cyclohexyl group, an octyl group or a dodecyl group, etc.), a substituted or unsubstituted aryl group (for example, a phenyl group or a tolyl group, etc.), a straight chain, branched chain or cyclic alkyl group containing an alkyloxy group (for example, a methoxy group, an ethoxy group, an isopropoxy group, a cyclohexyloxy group or an octyloxy group, etc.), a substituted or unsubstituted aryloxy group (for example, a phenoxy group, a p-tert-butylphenoxy group or a naphthoxy group, etc.), a N-sub
  • Y represents a substituted or unsubstituted aryl group (for example, a phenyl group, a 2-chlorophenyl group, a 4-chlorophenyl group, a 2,5-dichlorophenyl group, a 2,6-dichlorophenyl group, a 2,4,6-trichlorophenyl group, a 2-bromophenyl group, a 3,5-dibromophenyl group, a 2-cyanophenyl group, a 4-cyanophenyl group, a 3-nitrophenyl group, a 4-nitrophenyl group, a 4-methylphenyl group, a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a 4-butylphenyl group, a 2-trifluoromethylphenyl group, a 2-ethoxyphenyl group, a 2-phenylphenyl group, a 4-phenylphenyl group, a 4-
  • W represents a hydrophobic ballast group which preferably has 4 to 35 carbon atoms (more preferably, 8 to 32 carbon atoms) in order to render the coupler non-diffusible, which is linked directly or through an imino bond, an ether bond, a carbonamide bond, a sulfonamide bond, a ureido bond, an ester bond, an imide bond, a carbamoyl bond or a sulfamoyl bond, etc. to the aromatic nucleus of the anilino group.
  • Some examples of the ballast group are as shown in examples of the coupler of the present invention,
  • ballast group examples are as follows.
  • --CH 2 --CH(C 2 H 5 ) 2 For example, --CH 2 --CH(C 2 H 5 ) 2 , --C 12 H 25 , --C 16 H 33 and --C 17 H 33 .
  • V represents a hydrogen atom or a group defined for X or W.
  • Z represents a hydrogen atom or a group releasable upon a coupling reaction with an oxidized aromatic primary amino color developing agent, namely, a thiocyano group, an acyloxy group (for example, an acetoxy group, a dodecanoyloxy group, an octadecanoyloxy group, a 3-pentadecylphenoxy group, a benzoyloxy group, a ⁇ -naphthoyloxy group or a 3-[ ⁇ -(2,4-di-tert-amylphenoxy)butyramido]benzoyloxy group, etc.), an aryloxy group (for example, a phenoxy group, a p-chlorophenoxy group, a p-nitrophenoxy group or a naphthoxy group, etc.), an aralkyloxycarbonyl group (for example, a
  • Z may represent a group which is linked to a coupling position of the so-called colored couplers described in U.S. Pat. Nos. 2,455,170, 2,688,539, 2,725,292, 2,983,608 and 3,005,712 and British Pat. Nos. 800,262 and 1,044,778, etc., a group which is linked to a coupling position of the so-called development inhibiting compound releasable (DIR) couplers described in U.S. Pat. Nos. 3,148,062, 3,227,554 and 3,617,291, etc. or a group which is linked to a coupling position of couplers described in U.S. Pat. Nos. 3,006,759, 3,214,437, 3,311,476 and 3,419,391, etc.
  • DIR development inhibiting compound releasable
  • magenta couplers particularly preferred for use in the present invention an represented by the following formula ##STR14## wherein W and Z have the same meaning as defined in the formula (II), X 1 represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, a cyano group or a nitro group, and Y 1 represents a halogen atom, an alkyl group, an alkoxy group, a carboxyl group, a nitro group, an aryloxy group, a cyano group, an acylamino group, an alkoxycarbonyl group or an aryloxycarbonyl group.
  • Y 2 and Y 3 may be the same or different and each represent a hydrogen atom or a group defined in Y 1 .
  • Representative examples of the 3-anilino-5-pyrazolone type magenta couplers useful in the present invention are shown below, however, the present invention is not limited to these alone. ##STR15##
  • the compounds of formula (I) used in the present invention can be added to the photographic emulsions using well known techniques for coupler additions. Generally these techniques rely upon a high boiling point solvent or a high boiling point solvent and an auxiliary solvent. These solvents may be used for dispersing the compounds alone or together with the coupler.
  • Representative high boiling point solvents are described in U.S. Pat. No. 3,676,137 and include such solvents as butyl phthalate, dinonyl phthalate, butyl benzoate, diethylhexyl sebacate, butyl stearate, dinonyl maleate, tributyl citrate, tricresyl phosphate or dioctyl butyl phosphate, etc., diethyl succinate, dioctyl adipate, 3-ethylbiphenyl and liquid dye stabilizers described in "Product Licensing Index” Vol. 83, pages 26-29 (Mar. 1971) as "Improved photographic dye image stabilizer", etc.
  • organic solvents having a low boiling point used as auxiliary solvents together with the organic solvents having a high boiling point include ethyl acetate, butyl acetate, ethyl propionate, ethyl formate, butyl formate, nitromethane, carbon tetrachloride, chloroform, hexane, cyclohexane, ethylene glycol, acetone, ethanol, dimethylformamide and dioxane, etc. Further, benzene, toluene or xylene may be added to these solvents. These solvents are only an example and the present invention is not limited to them.
  • Surface active agents may be used to disperse the solution prepared by dissolving the compounds of the formula (I) alone or together with the coupler in an aqueous solution of a protective colloid.
  • Representative examples include saponin, sodium alkylsulfosuccinate and sodium alkylbenzene sulfonate, etc.
  • the hydrophilic protective colloids include gelatin, casein, carboxymethylcellulose, polyvinyl alcohol, polyvinyl pyrrolidone, styrene-maleic acid anhydride copolymer, condensates of styrene-maleic acid anhydride copolymer and polyvinyl alcohol, polyacrylates and ethylcellulose, etc.
  • the present invention is not limited to these.
  • the emulsion layer of the present invention may incorporate known magenta couplers besides the 3-anilino-5-pyrazolone coupler.
  • magenta couplers include pyrazolone type compounds, imidazolone type compounds and cyanoacetyl compounds. It is particularly advantageous to use pyrazolone type compounds.
  • magenta couplers include compounds described in U.S. Pat. Nos. 2,600,788, 2,983,608, 3,062,653, 3,127,269, 3,311,476, 3,419,391, 3,519,429, 3,558,319, 3,582,322, 3,615,506, 3,834,908 and 3,891,445, German Pat. No.
  • Couplers are used besides the magenta couplers.
  • Closed ring ketomethylene type compounds are generally used as yellow couplers. Examples include the compounds described in U.S. Pat. Nos. 3,341,331, 2,875,057 and 3,551,155, German Patent Application (OLS) No. 1,547,868, U.S. Pat. Nos. 3,265,506, 3,582,322 and 3,725,072, German Patent Application (OLS) No. 2,162,899, U.S. Pat. Nos. 3,369,895 and 3,408,194 and German Patent Application (OLS) Nos. 2,057,941, 2,213,461, 2,219,917, 2,261,361 and 2,263,875, etc.
  • Phenol or naphthol derivatives are mainly used as cyan couplers. Examples include the compounds described in U.S. Pat. Nos. 2,369,929, 2,474,293, 2,698,794, 2,895,826, 3,311,476, 3,458,315, 3,560,212, 3,582,322, 3,591,383, 3,386,301, 2,434,272, 2,706,684, 3,034,892, 3,583,971 and 3,933,500, German Patent Application (OLS) No. 2,163,811, Japanese Patent Publication No. 28836/70, etc.
  • DIR couplers such as those described in U.S. Pat. Nos. 3,227,554, 3,617,291, 3,701,783, 3,790,384 and 3,632,345, German Patent Application (OLS) Nos. 2,414,006, 2,454,301 and 2,454,329, British Pat. No. 953,454, Japanese Patent Application (OPI) Nos. 69624/77, 122335/74 and 69624/77 and Japanese Patent Publication No. 16141/76.
  • the emulsion layers in the present invention may contain compounds which release a development inhibitor upon development in addition to the DIR couplers.
  • compounds which release a development inhibitor upon development may contain compounds described in U.S. Pat. Nos. 3,297,445 and 3,379,529 and German Patent Application (OLS) No. 2,417,914.
  • an ultraviolet ray absorption layer is preferably used, because fading and discoloration by light are more effectively improved.
  • the present invention is not restricted with respect to the kind of color processing agents used.
  • Conventional agents may be used such as conventional color developers, bleaching agents stabilizers, etc.
  • intensifiers such as described in German Patent Application (OLS) No. 181,390, Japanese Patent Application (OPI) No. 9728/73 and U.S. Pat. No. 4,043,814.
  • the processes for preparing photographic silver halide emulsions and the photographic additives used in the color sensitive materials of the present invention are not restricted. It is possible to utilize the types of emulsions, water washings, chemical sensitization, antifogging agents and stabilizers, hardening agents, bases, plasticizers and lubricants, coating assistants, matting agents, sensitizers, spectral sensitizers, method of addition, absorption or filter dyes and methods of coating, etc. described in Research Disclosure No. 92 (Dec. 1971), pages 107-110.
  • the resulting emulsified dispersion was mixed with 145 g of a green-sensitive silver chlorobromide emulsion (Br: 50% by mol) (containing 7 g of Ag), and sodium dodecylbenzenesulfonate was added thereto as a coating assistant.
  • a green-sensitive silver chlorobromide emulsion Ba: 50% by mol
  • sodium dodecylbenzenesulfonate was added thereto as a coating assistant.
  • the emulsion was applied to a paper base the both surfaces of which were laminated with polyethylene (Sample A).
  • the amount of the coupler coated in Sample A was 400 mg/m 2 .
  • Samples B to G were produced by the same manner as in Sample A except that 3 g of the compound of the present invention or a comparison compound as shown in Table 1 was added at preparation in the same manner.
  • Each sample having the resulting dye image was subjected to a fading test for 5 days by means of a xenon tester (illuminance: 200,000 luxes) using an ultraviolet ray absorption filter produced by Fuji Photo Film Co. which cut rays of 400 nm and less.
  • the measurement was carried out by means of a Macbeth densitometer RD-514 (status AA filter), and the change in the density in areas having an initial magenta density of 2.0 was measured.
  • a coating composition for the third layer having a composition shown in the following Table III was prepared using the same compound as in Example 1 as a magenta coupler according to the process for producing Sample A in Example 1, and multilayer sample (Sample H) containing the third layer shown in Table III was produced. Further, multilayer samples (Samples I and J) were produced according to Sample H except that Compound (3) of the present invention was used in an amount of 3 g or 6 g based on 10 g of the same coupler. Further, samples of the present invention and comparative examples as shown in Table II were produced. These samples were exposed to light and developed in the same manner as in Example 1 to form images. Each sample was examined for 4 weeks by a fluorescent light fading tester (20,000 lux). The results are shown in Table II.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US06/105,485 1978-12-28 1979-12-20 Color photographic light-sensitive materials Expired - Lifetime US4273864A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP53-165359 1978-12-28
JP16535978A JPS5589836A (en) 1978-12-28 1978-12-28 Color photographic material

Publications (1)

Publication Number Publication Date
US4273864A true US4273864A (en) 1981-06-16

Family

ID=15810861

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/105,485 Expired - Lifetime US4273864A (en) 1978-12-28 1979-12-20 Color photographic light-sensitive materials

Country Status (7)

Country Link
US (1) US4273864A (enrdf_load_stackoverflow)
JP (1) JPS5589836A (enrdf_load_stackoverflow)
BE (1) BE880944A (enrdf_load_stackoverflow)
CA (1) CA1142013A (enrdf_load_stackoverflow)
DE (1) DE2952549A1 (enrdf_load_stackoverflow)
FR (1) FR2445542A1 (enrdf_load_stackoverflow)
GB (1) GB2042199B (enrdf_load_stackoverflow)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0098241B1 (de) * 1982-06-16 1985-10-02 Ciba-Geigy Ag Hydrochinonäther und ein Verfahren zu deren Herstellung

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2735765A (en) * 1953-06-03 1956-02-21 Ch-chs
US3907571A (en) * 1972-11-15 1975-09-23 Fuji Photo Film Co Ltd Magenta coupler-containing silver halide photographic materials
US3982944A (en) * 1974-02-06 1976-09-28 Fuji Photo Film Co Ltd Antifoggant dispersion for color photographic materials

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5448538A (en) * 1977-09-12 1979-04-17 Konishiroku Photo Ind Co Ltd Color photographic material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2735765A (en) * 1953-06-03 1956-02-21 Ch-chs
US3907571A (en) * 1972-11-15 1975-09-23 Fuji Photo Film Co Ltd Magenta coupler-containing silver halide photographic materials
US3982944A (en) * 1974-02-06 1976-09-28 Fuji Photo Film Co Ltd Antifoggant dispersion for color photographic materials

Also Published As

Publication number Publication date
JPS6152463B2 (enrdf_load_stackoverflow) 1986-11-13
DE2952549A1 (de) 1980-10-09
FR2445542A1 (fr) 1980-07-25
GB2042199A (en) 1980-09-17
GB2042199B (en) 1983-01-26
BE880944A (fr) 1980-04-16
JPS5589836A (en) 1980-07-07
CA1142013A (en) 1983-03-01

Similar Documents

Publication Publication Date Title
US3615506A (en) Silver halide emulsions containing 3-cyclicamino-5-pyrazolone color couplers
US3935015A (en) Silver halide color photographic materials containing 3-anilino-5-pyrazolane couplers
US4584264A (en) Color photographic light-sensitive materials
US4732845A (en) Silver halide color photographic materials
US4193802A (en) Silver halide photographic light-sensitive material containing aromatic ester solvent
JPS6186750A (ja) 写真記録材料
US3935016A (en) Silver halide color photographic materials containing 3-anilino-5-pyrazolone couplers
US4346165A (en) Process for improving light fastness of color images
US4332886A (en) Color photographic light-sensitive material including an organic spirobis compound color coupler
JPS6245545B2 (enrdf_load_stackoverflow)
US4525451A (en) Color photographic light-sensitive material comprising phenol or naphthol having sulfamoylamino group
US4108663A (en) Photographic developing agents, process for developing using same, and light-sensitive materials containing same
US4133686A (en) Color photographic light-sensitive element
US4345024A (en) Photographic development inhibitor releasing compound
US4587210A (en) Color photographic silver halide light-sensitive material consisting of a specified hydroquinone derivative
US4264720A (en) Color photographic light-sensitive material
US4266020A (en) Color photographic light-sensitive material
EP0125522B1 (en) Color photographic materials
US4668610A (en) 2-equivalent cyan dye-forming 5-hydroxy-6-acylamino-benzoxazole-2-one couplers, silver halide photographic elements and processes employing them
US4273864A (en) Color photographic light-sensitive materials
US4199361A (en) Color photographic light-sensitive element
US4552836A (en) Silver halide color photographic light-sensitive material
US4200464A (en) Silver halide color photographic materials containing a UV filter compound
US4279990A (en) Color photographic materials
CA1122842A (en) Color photographic light-sensitive material containing 2,5-bis (1,1'-dimethylbutyl) hydroquinone and a 3-anilino 5-pyrazolone magenta coupler

Legal Events

Date Code Title Description
STCF Information on status: patent grant

Free format text: PATENTED CASE